Process for the production of isosolanone and solanone, intermediates useful in said process and organoleptic uses of said intermediates

ABSTRACT

Described is a novel genus of compounds defined according to the structure: ##STR1## wherein Z represents hydrogen, MgX and the moiety having the structure: ##STR2## and X represents chlor, bromo, or iodo; as well as 5-isopropyl-8-methyl-5,8-nonadien-2-one; uses of same as intermediates in a process for producing isosolanone and solanone; and organoleptic uses of 5-isopropyl-8-methyl-5,8-nonadien-2-one and 2,6-dimethyl-5-methylene-1-hepten-4-ol. 
     The novel process of our invention involved the steps of: 
     (i) formation of the compound having the structure: ##STR3##  by means of reacting 3-methyl-2-methylenebutanal with the compound having the structure: ##STR4## (ii) acid hydrolysis of the resulting compound in order to form 2,6-dimethyl-5-methylene-1-heptene-4-ol; 
     (iii) reaction of 2,6-dimethyl-5-methylene-1-hepten-4-ol with methyl aceto acetate in order to form 2,6-dimethyl-5-methylene-1-hepten-4-yl aceto acetate or, directly, 5-isopropyl-8-methyl-5,8-nonadiene-2-one; 
     (iv) reacting 2,6-dimethyl-5-methylene-1-hepten-4-yl aceto acetate in the presence of an appropriate catalyst to form the 5-isopropyl-8-methyl-5,8-nonadiene-2-one; and 
     (v) isomerizing the 5-isopropyl-8-methyl-5,8-nonadien-2-one in order to form a mixture of solanone and the isosolanone or 5-isopropyl-8-methyl-5,8-nonadiene-2-one.

This is a divisional of application Ser. No. 542,477, filed Oct. 17,1983, now U.S. Pat. No. 4,476,147 which, in turn, is a divisional ofU.S. Letters Patent, Ser. No. 380,542 filed May 20, 1982 now U.S. Pat.No. 4,433,695 issued Feb. 28, 1984.

BACKGROUND OF THE INVENTION

Solanone is known as a useful tobacco flavorant and flavor enhancer. Itis a mixture consisting primarily of the compounds defined according tothe structure: ##STR5## which is indicative of a cis and trans mixtureof compounds having the structures: ##STR6##

Isosolanone, an isomer of solanone, is a mixture of cis and transisomers defined according to the structure: ##STR7## which is indicativeof a mixture of cis and trans isomers having the structures: ##STR8##

Isosolanone and solanone are disclosed in a paper by Demole and Berthetentitled "A Chemical Study of Burley Tobacco Flavour (Nicotiana tabacumL.) I. Volatile to medium-volatile constituents", Helvetica ChimicaActa, Volume 55, Fasc. 6(1972) Nr. 175-176, pages 1866-1882, to bepresent in burley tobacco aroma.

A need has arisen, however, to produce in an economical and efficientmanner solanone and isosolanone. The paper by Johnson and Nicholsonentitled "The Structure, Chemistry and Synthesis of Solanone, A NewAnomalous Terpenoid Ketone from Tobacco" published in J. Org. Chem.30(9), 2918-21 (1965) discloses a rather complex synthesis for solanoneand isosolanone.

Furthermore, in the perfumery art there is a considerable need forconstituents having minty, herbal, anisic, cedarleaf, and pennyroyalaroma nuances with floral and coriander-like undertones.

Such fragrance materials have a wide utilization in the presence of theperfumery compound of our invention. A limited amount of such materialsthat give rise to these properties is available from natural sources butthe natural materials are subject to wide variations in quality, areexpensive and are often in critically short supply.

In addition, there is a continuing search for food flavor compositionswhich can vary, fortify, modify, enhance, augment or otherwise improvethe flavor and/or aroma of foodstuffs, medicinal products, toothpastesand chewing gums. To be satisfactory, such compositions should bestable, non-toxic and blendable with other ingredients to provide theirown unique flavor and aroma nuances without detracting from thecoingredients. Preferably such compositions should be naturallyoccurring or present in natural foodstuffs so that their ingestiblesafety can be readily recognized. These materials should be capable ofbeing synthesized in a simple and economical manner. The need for safeflavors in the cooked vegetable flavor area and in the garlic area iswell known. More specifically, there is a need for development ofnon-toxic materials which can replace natural materials not readilyavailable having floral, patchouli-like, cooked red beet-like, earthy,garlic and green aroma and taste characteristics.

The instant invention provides the foregoing which the prior art hasheretofore failed to provide. Furthermore, nothing in the prior artshows the unexpected, unobvious and advantageous value of the compoundshaving the structures: ##STR9## wherein Z represents hydrogen, MgX or:##STR10## and X represents chloro, bromo or iodo or of the compounddefined according to the structure: ##STR11## which is indicative of amixture of cis and trans isomers having the structures: ##STR12##

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for bulked fractions 1-4 of the distillationproduct of the reaction product of Example I containing the compoundhaving the structure: ##STR13##

FIG. 2 is the NMR spectrum for fraction 2 of the distillation product ofthe reaction product of Example I containing the compound having thestructure: ##STR14## (Solvent: CFCl₃ ; Field strength: 100 MHz).

FIG. 3 is the GLC profile for bulked fractions 5-7 of the distillationproduct of the reaction product of Example II containing the compoundhaving the structure: ##STR15##

FIG. 4 is the NMR spectrum for fraction 3 of the distillation product ofthe reaction product of Example II containing the compound having thestructure: ##STR16## (Solvent: CFCl₃ ; Field Strength: 100 MHz).

FIG. 5 is the GLC profile for bulked fractions 7-11 of the distillationproduct of the reaction product of Example V(A) containing a mixture ofcis and trans isomers of compounds defined according to the structure:##STR17## or defined according to the structures: ##STR18##

FIG. 6 is the GLC profile for the reaction product of Example VI(A)containing the cis and trans isomers of compounds defined according tothe structure: ##STR19## or according to the structures: ##STR20##

FIG. 7 is the NMR spectrum for the peak indicated by the referencenumeral "61" of FIG. 6 for the cis or the trans isomer of the compoundsdefined according to the structure: ##STR21## (Solvent: CFCl₃ ; Fieldstrength: 100 MHz).

FIG. 8 is the NMR spectrum for the peak indicated by reference numeral"62" on FIG. 6 for the cis or the trans isomer of the compounds definedaccording to the structure: ##STR22##

FIG. 9 is the GLC profile for the reaction product of Example VII(A)analyzed as a mixture containing the compounds having the structures:##STR23##

FIG. 10 is the NMR spectrum for the peak indicated by reference numeral"91" on FIG. 9; analyzed as a mixture of the compounds having thestructures: ##STR24## (Solvent: CFCl₃ ; Field strength: 100 MHz).

FIG. 11 is the GLC profile for bulked fractions 4-11 of the distillationproduct of the reaction product of Example VII(B) containing thecompound having the structure: ##STR25##

FIG. 12 is the NMR spectrum for the compound of fraction 7 of thedistillation product of the reaction product of Example VII(B)containing the compound having the structure: ##STR26## (Solvent: CFCl₃; Field strength: 100 MHz).

FIG. 13 is the infra-red spectrum for fraction 7 of the distillationproduct of the reaction product of Example VII(B) for a mixture of cisand trans isomers of the compounds defined according to the structure:##STR27##

FIG. 14 is the GLC profile for bulked fractions 9-12 of the distillationproduct of the reaction product of Example IX containing a mixture ofcis and trans isomers of the compounds defined according to thestructure: ##STR28##

FIG. 15 is the NMR spectrum for the peak indicated by reference numeral"141" of FIG. 14 for the cis or trans isomer of the compounds definedaccording to the structure: ##STR29## (Solvent: CFCl₃ ; Field strength:100 MHz).

FIG. 16 is the NMR spectrum for the peak indicated by reference numeral"142" on FIG. 14 which is for the cis or trans isomer of the compoundsdefined according to the structure: ##STR30## (Solvent: CFCl₃ ; Fieldstrength: 100 MHz).

DETAILED DESCRIPTION OF THE DRAWINGS

In FIG. 6, the peaks indicated by reference numerals "61" and "62" arefor the cis and trans isomers of the compounds defined according to thestructure: ##STR31## Thus, the peak indicated by reference numeral "61"is for the cis or trans isomer of the compounds defined according to thestructure: ##STR32## and the peak indicated by reference numeral "62" isfor the cis or trans isomer of the compounds defined according to thestructure: ##STR33##

FIG. 9 is the GLC profile for the reaction product of Example VII(A).The peak indicated by reference numeral "91" is a peak analyzed as amixture of compounds; the first compound having the structure: ##STR34##and the second compound having the structure: ##STR35##

FIG. 14 is the GLC profile for bulked fractions 9-12 of the distillationproduct of the reaction product of Example IX (conditions: SE-30 columnprogrammed at 100°-220° C. at 8° C. per minute) for the cis and transisomer mixtures of compounds defined according to the structures:##STR36##

The peak indicated by reference numeral "141" is the peak for the cis orthe trans isomer of the compounds having the structure: ##STR37##

The peak indicated by the reference numeral "142" is for the cis or thetrans isomer of the compounds having the structure: ##STR38##

THE INVENTION

The present invention provides an efficient low cost process forproducing isosolanone which is a mixture of cis and trans isomersdefined according to the structure: ##STR39## or shown by thestructures: ##STR40## as well as solanone, a mixture of cis and transisomers defined according to the structure: ##STR41## also shown by thestructures: ##STR42##

In addition, the present invention provides organoleptically usefulintermediates resulting from the practice of said process. Theorganoleptically useful intermediates have the structures: ##STR43## amixture of cis and trans isomers also shown by the structures: ##STR44##as well as: ##STR45##

The present invention also provides the genus of novel compounds whichare defined according to the structure: ##STR46##

(sometimes referred to herein as "Structure 5")

wherein Z represents hydrogen, MgX or the moiety having the structure:##STR47## and wherein X represents chloro, bromo or iodo. When Z ishydrogen, the compound defined according to the structure: ##STR48##actually has the structure: ##STR49## which is as stated supra usefulfor its organoleptic properties in addition to being useful as anintermediate in the production of solanone or isosolanone.

The compound having the structure: ##STR50## is capable of augmenting orenhancing red beet flavors and nuances that relate to same includingpatchouli-like and earthy aroma and taste nuances. This compound havingthe structure: ##STR51## is also useful in augmenting or enhancing theminty, herbal, anisic, cedarleaf and pennyroyal-like aromas with floraland coriander undertones of perfumes, colognes and perfumed articles.

The mixture of cis and trans isomers of the compounds defined accordingto the structure: ##STR52## is useful for augmenting or enhancing thearoma or taste of alliaceous flavors, particularly garlic flavors, byaugmenting or enhancing the garlic and green aroma and taste nuances ofalliaceous-flavored foodstuffs.

The economic straightforward process of our invention may be describedby the following sequence of reactions:

REACTION I ##STR53## REACTION II ##STR54## (wherein X represents chloro,bromo or iodo). REACTION III ##STR55## (in one step or via theintermediates: ##STR56## REACTION IV ##STR57##

In carrying out Reaction I: ##STR58## any secondary amine can be used asa catalyst. The formaldehyde source may be para formaldehyde, formalinor trioxane but formalin is the preferred formaldehyde source. Thereaction pressure may be atmospheric or super-atmospheric butatmospheric pressure is preferred. The reaction temperature range isfrom about 60° C., up to about 100° C. with a preferred range of 75°-80°C. In addition, Mannich-type reaction conditions using an amine saltcatalyst or normal "aldol"-type conditions using sodium hydroxide orbarium hydroxide may also be used. The isovaleraldehyde:formaldehydemole ratio may vary from about 1:10 up to about 10:1 with a preferredrange of mole ratio of isovaleraldehyde:formaldehyde being from 1:1 upto about 1:1.1. The mole ratio of isovaleraldehyde:catalyst may varyfrom about 1:1 down to about 1:0.01 with a preferred mole ratio ofisovaleraldehyde:catalyst being from about 1:0.1 down to about 1:0.05.

With reference to the Reaction II sequence: ##STR59## the mole ratio of2-isopropylpropenal:methallyl halide (which becomes the methallylGrignard reagent) may vary from about 1:1 to about 1:1.5 and the moleratio of magnesium metal:methallyl halide may vary from about 0.1:1 upto about 1.5:1.

The methallyl halide reagent may be methallyl chloride, methallylbromide or methallyl iodide with methallyl chloride being the preferredreagent. The reaction is carried out in a solvent which is inert to thereactants in the desired reaction temperature range (0° C. up to about150° C.; at 1 up to about 100 atmospheres pressure). Thus, the solventused may be diethylether, di-n-butylether, tetrahydrofuran, other ethersor mixtures of ethers and inert co-solvents (e.g. xylene, toluene orbenzene). The preferred solvent is tetrahydrofuran. The hydrolysis maybe carried out in the presence of any acid such as dilute hydrochloricacid, aqueous ammonium chloride, dilute sulfuric acid or dilute aceticacid.

The resulting compound having the structure: ##STR60## produced byhydrolysis of the compound having the structure: ##STR61## wherein X ischloro, bromo or iodo, may be carefully distilled (via fractionaldistillation) and used "as is" for its organoleptic properties inaugmenting or enhancing the aroma or taste of perfume compositions,colognes, perfumed articles, foodstuffs, chewing gums, toothpastes,medicinal products or chewing tobaccos. In the alternative, the compoundhaving the structure: ##STR62## may be further reacted.

Thus, in the Reaction III: ##STR63## wherein R represents C₁ -C₄ loweralkyl, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl or t-butyl,this reaction may take place in one step or it may take place in twosteps forming an intermediate ketoester having the structure: ##STR64##thusly:

REACTION IIIA ##STR65## REACTION IIIB ##STR66##

In carrying out Reaction IIIA, ##STR67## the catalyst used is aluminumtriisopropylate. The mole ratio of alcohol 4:ketoester may vary fromabout 1:5 up to about 2:1. The mole ratio of alcohol 4:aluminumtriisopropylate may vary from about 100:1 down to about 5:1. Theco-solvent used may be any inert material which allows the desiredtemperature to be achieved such as toluene or xylene. A co-solvent isnot necessary and the preferred process would not be used in conjunctionwith such a co-solvent. At the end of the reaction, the reaction productmay be "worked-up" and distilled or the crude product may be used as iswithout distillation for further reaction to form the compound havingthe structure: ##STR68##

The preferred ketoester having the structure: ##STR69## is methyl orethyl acetoacetate.

In the Reaction IIIB: ##STR70## to form the mixture of cis and transisomers of the compounds having the structure: ##STR71## the catalystused may be aluminum triisopropylate or sodium carbonate/polyethyleneoxide. If aluminum isopropylate is used as a catalyst, either no solventor a high boiling solvent (e.g. decalin) may be used. If sodiumcarbonate is used, then N-methyl-2-pyrrolidinone is the preferredsolvent. The reaction temperature may vary from about 150° C. up toabout 200° C. When using aluminum triisopropylate as a catalyst, themole ratio of aluminum triisopropylate:ketoester having the structure:##STR72## may vary from about 1:100 down to 1:5. When using sodiumcarbonate as a catalyst, the mole ratio of sodium carbonate:ketoesterhaving the structure: ##STR73## may vary from about 1:20 down to 1:2.

The resulting product may be "worked-up" and distilled as by fractionaldistillation particularly if it is desired to use the product "as is"for its organoleptic properties in augmenting or enhancing the taste ofalliaceous-flavored foodstuffs. The resulting product may be used"crude" after stripping the solvent for the next reaction, however.

In carrying out the Reaction IV to form the mixtures of cis and transisomers defined according to the structures: ##STR74## that is, thereaction: ##STR75## the catalyst used may be para-toluenesulfonic acidor any other strong mineral acid, e.g. phosphoric acid or sulfuric acid.Preferred is para-toluenesulfonic acid, however. The co-solvent used maybe any suitably inert material which allows the achievement of thedesired reaction temperature. Among such preferred solvents are tolueneor xylene. The reaction temperature may be in the range of from about40° C. up to about 150° C. The preferred reaction temperature range isfrom about 100° C. to about 120° C. in order to optimize the time ofreaction and maximize the yield of product.

The mole ratio of protonic acid compound having the structure 3 may varyfrom about 1:100 down to 1:10. The weight ratio of solvent:compoundhaving the structure 3 may vary from about 100:1 down to about 1:10 witha preferred weight ratio of solvent:compound having the structure 3being 1:1. The resulting reaction product may be "worked-up" andfractionally distilled to yield individually compounds 1 and 2 ormixtures of both compounds (mixtures of cis and trans isomers) havingthe structures: ##STR76##

Each of these compounds 1 and 2 and mixtures containing both compoundshave organoleptic uses in augmenting or enhancing the aroma or taste ofconsumable materials including foodstuffs, chewing gums, toothpastes,smoking tobaccos, medicinal products, perfumes, colognes, perfumedarticles, (e.g. solid or liquid anionic, cationic, nonionic orzwitterionic detergents, perfumed polymers, hair preparations, cosmeticpowders and the like), smoking tobacco products and smoking tobaccos.

The Reaction I: ##STR77## is basically described in the literature(Chem. Abstracts 93:238810j and 93:185765q).

In the Reaction sequence II: ##STR78## it is preferred that the compoundhaving the structure: ##STR79## and methallyl chloride be addedsimultaneously to magnesium. The methallyl Grignard reagent is preferredto be formed in situ and is preferred to be consumed as rapidly as it isformed. This avoids or reduces the usual problems associated withallylic Grignards including lower yields due to coupling and need forhigh dilution and low temperature to avoid coupling when synthesizingthe Grignard reagent.

In place of aluminum triisopropylate used as a catalyst in the ReactionIIIA: ##STR80## any mildly basic catalyst is usable, but the aluminumtriisopropylate is the preferred catalyst. In the alternative, in placeof using the ketoester having the structure: ##STR81## diketene may beused.

The Reaction sequences IIIA and IIIB: ##STR82## together constitute anexample of the "Carrol reaction", and such a reaction is set forth inJ.C.S., 1266(1940).

The Reaction IV: ##STR83## was previously reported using apara-toluenesulfonic acid-ethanol system. Under these conditions, theisosolanone forms a number of non-volatile materials which areantithetical to utility for their organoleptic properties. Using thepara-toluenesulfonic acid-toluene or xylene system yields goodisomerization to the cis and trans isosolanone defined according to thestructure: ##STR84## a highly desirable product useful for itsorganoleptic properties in augmenting or enhancing the aroma or taste ofsmoking tobacco or smoking tobacco articles or components of smokingtobacco articles such as the filter and the wrapper.

When one of the compounds: ##STR85## (mixture of cis or trans isomers)or ##STR86## (hereinafter collectively termed "oxo derivatives") areused taken alone or together as food flavor adjuvants, the nature of theco-ingredients included with said oxo compound(s) will also serve toalter, modify, augment or enhance the organoleptic characteristics ofthe ultimate foodstuff treated therewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,diary products, candies, chewing gums, vegetables, cereals, soft drinks,snacks and the like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay, rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g. glycerine, and a flavoring composition whichincorporates the oxo compound(s) of our invention, and in addition,sweetening agents which may be sugars, including sucrose or dextroseand/or artificial sweeteners such as cyclamates or saccharin. Otheroptional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g. sodium chloride;antioxidants, e.g. calcium and sodium ascorbate, ascorbic acid,butylated bydroxy-anisole (mixture of 2- and3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g. citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g. agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth, gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins and emulsifiers, e.g. mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g. sucrose, corn syrup and the like.

Surface active agents include emulsifying agents, e.g. fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g. benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like;starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g. sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g. carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate, texturizers, anti-caking agents, e.g. aluminumcalcium sulfate and tribasic calcium phosphate, enzymes; yeast foods,e.g. calcium lactate and calcium sulfate; nutrient supplements, e.g.iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methylbutyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g. acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methyl butanal,beta,beta-dimethyl-acrolein, methyl-n-amyl ketone, n-hexenal, 2-hexenal,2-hexenal, isopentanal, hydrocinnamic aldehyde, cis-3-hexenal,2-heptanal, nonyl aldehyde, 4-(p-hydroxyphenyl)-2-butanone,alpha-ionone, beta-ionone, methyl-3-butanone, benzaldehyde, damascone,damascenone, acetophenone, 2-heptanone, o-hydroxyacetophenone,2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal,2-phenyl-2-hexenal, 2-phenyl-2-pentenal, furfural, 5-methyl furfural,cinnamaldehyde, beta-cyclohomocitral, 2-pentanone, 2-pentenal andpropanal; alcohols such as 1-butanol, benzyl alcohol, 1-borneol,trans-2-buten-1-ol, ethanol, geraniol, 1-hexanal, 2-heptanol,trans-2-hexenol-1, cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol,1-penten-3 -ol, p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchylalcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate,eugenol, linalool, 2-heptanol, acetoin; esters, such as butyl acetate,ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as naphthalene, myrcene, naphthalene, octadecane, tetradecane,tetramethyl naphthalene, tridecane, trimethyl naphthalene, undecane,caryophyllene, 1-phellandrene, p-cymene, 1-alphapinene; pyrazines suchas 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils,such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute,orris absolute, lemon essential oil, Bulgarian rose, yara yara andvanilla; lactones such as δ-nonalactone; sulfides, e.g. methyl sulfidesand alkyl-alkenyl di- and trisulfides as set forth in U.S. Pat. No.3,615,601 the specification for which is incorporated herein byreference, and other materials such as maltol, acetoin and acetals (e.g.1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e. foodstuff, whether simulated or natural, and should, in any event(i) be organoleptically compatible with the oxo compound(s) of ourinvention by not covering or spoiling the organoleptic properties (aromaand/or taste) thereof; (ii) be non-reactive with the oxo compound(s) ofour invention and (iii) be capable of providing an environment in whichthe oxo compound(s) of our invention can be dispersed or admixed toprovide a homogeneous medium. In addition, selection of one or moreflavoring adjuvants, as well as the quantities thereof will depend uponthe precise organoleptic character desired in the finished product.Thus, in the case of flavoring compositions, ingredient selection willvary in accordance with the foodstuff, chewing gum, medicinal product ortoothpaste to which the flavor and/or aroma are to be imparted,modified, altered or enhanced. In contradistinction, in the preparationof solid products, e.g. simulated foodstuffs, ingredients capable ofproviding normally solid compositions should be selected such as variouscellulose derivatives.

As will be appreciated by those skilled in the art, the amount of theoxo compound(s) employed in a particular instance can vary over arelatively wide range, depending upon the desired organoleptic effectsto be achieved. Thus, correspondingly greater amounts would be necessaryin those instances wherein the ultimate food composition to be flavoredis relatively bland to the taste, whereas relatively minor quantitiesmay suffice for purposes of enhancing the composition merely deficientin natural flavor or aroma. The primary requirement is that the amountselected be effective, i.e. sufficient to alter, modify or enhance theorganoleptic characteristics of the parent composition, whetherfoodstuff per se, chewing gum per se, medicinal product per se,toothpaste per se, or flavoring composition.

The use of insufficient quantities of the oxo compound(s) will, ofcourse, substantially vitiate any possibility of obtaining the desiredresults while excess quantities prove needlessly costly and in extremecases, may disrupt the flavor-aroma balance, thus provingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded as significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of the oxo compound(s) rangingfrom a small but effective amount e.g. 0.05 parts per million up toabout 100 parts per million based on total composition are suitable.Concentrations in excess of the maximum quantity stated are not normallyrecommended, since they fail to provide commensurate enhancement oforganoleptic properties. In those instances wherein the oxo compound(s)is added to the foodstuff as an integral component of a flavoringcomposition, it is, of course, essential that the total quantity offlavoring composition employed be sufficient to yield an effectiveconcentration of the oxo compound(s) in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the oxo compound(s) in concentrationsranging from about 0.1% up to about 15% by weight based on the totalweight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the oxo compounds(s) with, for example,gum arabic, gum tragacanth, carrageenan and the like, and thereafterspray-drying the resultant mixture whereby to obtain the particularsolid product. Pre-prepared flavor mixes in powder form, e.g. afruit-flavored powder mix are obtained by mixing the dried solidcomponents, e.g. starch, sugar and the like and the oxo compound(s) in adry blender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with the oxo compound(s) of ourinvention, the following adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Cassia oil;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Eugenol;

Vanillin;

Carryophyllene;

Methyl cinnamate;

Guiacol;

Ethyl pelargonate;

Cinnamaldehyde;

Methyl Anthranilate;

5-Methyl furfural;

Isoamyl acetate;

Isobutyl acetate;

Cuminaldehyde;

Alpha ionone;

Cinnamyl formate;

Ethyl butyrate;

Methyl cinnamate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Furfural;

Ethyl acetate;

Anethole;

2,3-Dimethyl pyrazine;

2-Ethyl-3-methyl pyrazine;

3-Phenyl-4-pentenal;

2-Phenyl-2-hexenal;

2-Phenyl-2-pentenal;

3-Phenyl-4-pentenal diethyl acetal;

β-Damascone (1-crotonyl-2,2,6-trimethylcyclohex-1-ene);

β-Damascenone(1-crotonyl-2,2,6-trimethylcyclohexa-1,3-diene);

Beta-cyclohomocitral(2,2,6-trimethylcyclohex-1-ene carboxaldehyde);

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine (4-allyl-1,2,6-trimethoxybenzene);

Isoelemecine (4-propenyl-1,2,6-trimethoxybenzene); and

2-(4-Hydroxy-4-methylpentyl)norbornadiene prepared according to U.S.Pat. No. 3,886,289 issued on May 27, 1975

Methyl(2-methyl propenyl)trisulfide;

Propenyl(2-methyl propenyl)trisulfide;

Ethyl(2-ethyl propenyl)trisulfide;

Methyl propenyl trisulfide;

Propyl propenyl trisulfide;

Methyl-propyl disulfide;

Methyl-propenyl disulfide;

Dipropyl-disulfide;

Propyl-propenyl disulfide;

Diallyl-disulfide;

Dimethyl-disulfide.

The compound having the structure: ##STR87## and one or more auxiliaryperfume ingredients including, for example, alcohols (other than thecompound having the structure): ##STR88## aldehydes, ketones, terpinichydrocarbons, nitriles, esters, lactones, natural essential oils andsynthetic essential oils may be admixed so that the combined odors ofthe individual components produce a pleasant and desired fragrance,particularly and preferably in floral fragrances. Such perfumecompositions usually contain (a) the main note or the bouquet orfoundation stone of the composition; (b) modifiers which round off andaccompany the main note; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all stages ofevaporation and substances which retard evaporation and (d) topnoteswhich are usually low-boiling, fresh-smelling materials.

In perfume compositions, it is the individual component which contributeto their particular olfactory characteristics, however, the overallsensory effect of the perfume composition will be at least the sum totalof the effects of each of the ingredients. Thus, the compound having thestructure: ##STR89## can be used to alter, modify or enhance the aromacharacteristics of a perfume composition, for example, by utilizing ormoderating the olfactory reaction contributed by another ingredient inthe composition.

The amount of the compound having the structure: ##STR90## of ourinvention which will be effective in perfume compositions as well as inperfumed articles and colognes depends on many factors including theother ingredients, their amounts and the effects which are desired. Ithas been found that perfume compositions containing as little as 0.01%of the compound having the structure: ##STR91## and as much as 50% ofthis compound can be used to impart a minty, herbal, anisic, cedarleaf,and pennyroyal-like aroma profile with floral and coriander-likeundertones to perfume compositions, perfumed articles and colognes. Theamount employed can range up to 70% of the fragrance components and willdepend on considerations of cost, nature of the end product, the effectdesired on the finished product and the particular fragrance sought.

The compound having the structure: ##STR92## (taken alone or furthertogether with other ingredients in perfume compositions) may be used asan olfactory component in solid or liquid anionic, cationic, nonionic orzwitterionic detergents and soaps, perfumed polymers such as perfumedpolyethylene and perfumed polyurethanes, space odorants and deodorants,perfumes, colognes, toilet water, bath preparations such as creams,deodorants, hand lotions and sun screens, powders such as talcs, dustingpowders, face powders and the like. When used as an olfactory componentin perfumed articles,

as little as 0.001% of the compound having the structure: ##STR93## willsuffice to impart an intense, minty, herbal, anisic, cedarleaf andpennyroyal-like aroma profile with coriander undertones to floralfragrance formulations including rose formulations. Generally, no morethan 3% of the compound having the structure: ##STR94## based on theultimate end product is required. Thus, the range of use in perfumedarticles of the compound having the structure: ##STR95## may vary from0.001% up to 3% by weight of the perfumed article.

In addition, the perfumed composition or fragrance composition of ourinvention can contain a vehicle or carrier for the compound having thestructure: ##STR96## The vehicle can be a liquid such as a non-toxicalcohol, a non-toxic glycol or the like. An example of such a non-toxicalcohol is ethyl alcohol. Examples of such non-toxic glycols are1,2-propylene glycol or 2,3-butylene glycol. The carrier can also be anabsorbent solid such as a gum (e.g. gum arabic, xanthan gum, guar gum ormixtures of same) or components for encapsulating the composition, suchas gelatin (as by coacervation) or a urea-formaldehyde prepolymer, wherea polymer capsule wall is formed around a liquid perfume compositioncenter.

Furthermore, the compounds defined according to the structures:##STR97## produced according to the process of our invention are capableof supplying or potentiating certain flavor and aroma notes usuallylacking in many tobacco flavors heretofore provided.

As used herein in regard to tobacco flavors, the terms "alter" and"modify" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland tobacco, tobacco substituents ortobacco flavor formulations or agumenting the existing flavorcharacteristics where a natural flavor is deficient in some regard orsupplementing the existing flavor impression to modify its quality,character or taste".

As used herein, the term "enhance" is intended to mean theintensification (without change in kind of quality of aroma or taste) ofone or more taste and/or aroma nuances present in the organolepticimpression of tobacco or a tobacco substitute or a tobacco flavor.

Our invention thus provides an organoleptically improved smoking tobaccoproduct and additives therefor, as well as methods of making same whichovercome specific problems heretofore encountered in which specificdesired musty, oily, slightly green, heavy, full-bodied burley tobaccocharacter are created or enhanced and may be readily controlled andmaintained at the desired uniform level regardless of variations in thetobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby various musty, oily, slightly green, tobacco-like, full-bodiedburley tobacco aroma and taste notes may be imparted to smoking tobaccoproducts and may be readily varied and controlled to produce the desireduniform flavor characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g. dried lettuce leaves)an aroma and flavor additive containing as an active ingredient the5-isopropyl-8-methyl-5,7-nonadien-2-one cis and trans isomer mix definedaccording to the structure: ##STR98## of our invention. In addition tothe mixture of cis and trans isomers of the compounds defined accordingto the structure: ##STR99## other flavor and aroma additives may beadded to the smoking tobacco materials or substitute therefor eitherseparately or in admixture with the cis and trans isomers of thecompounds defined according to the structure: ##STR100## as follows: (i)Synthetic materials:

Beta-ethyl-cinnamaldehyde;

Beta-cyclohomocitral;

Eugenol;

Dipentene;

Beta-damascenone;

Beta-damascone;

Alpha-damascone;

Gamma-damascone;

Trans,trans delta-damascone produced according to U.S. Pat. No.4,211,242

Maltol;

Ethyl maltol;

Delta-undecalactone;

Delta-decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxy-ethyl)decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1,b]furan;

4-Hydroxy hexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

(ii) Natural oils:

Celery seed oil;

Coffee extract;

Bergamot oil;

Cocoa extract;

Nutmeg oil;

Origanum oil.

An aroma and flavoring concentrate containing a mixture of cis and transisomers of the compounds defined according to the structure: ##STR101##or a composition containing a mixture of the compounds defined accordingto the structure: ##STR102## with a mixture of cis and trans isomershaving the structures: ##STR103## and, if desired, one or more of theabove indicated additional flavoring additives may be added to thesmoking tobacco material, to the filter or to the leaf or paper wrapper.The smoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g. lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as enhancement or the imparting of natural and/or rich burleynotes, we have found that satisfactory results are obtained if theproportion by weight of the sum total of the composition containing amixture of cis and trans isomers of the compounds having the structure:##STR104## to smoking tobacco material is between 150 ppm and 1,500 ppm(0.015%-0.15%) of the active ingredients to the smoking tobaccomaterial. We have further found that satisfactory results are obtainedif the proportion by weight of the mixture of cis and trans isomers ofthe compounds having the structure: ##STR105## to additional flavoringmaterial in the flavor composition is between 1,500 and 15,000 ppm(0.15%-1.5%).

Any convenient method for incorporating the mixture of cis and transisomers of the compounds defined according to the structure: ##STR106##in the tobacco product may be employed. Thus the mixture of cis andtrans isomers of the compounds defined according to the structure:##STR107## or the mixtures of cis and trans isomers containing thecompounds having the structures: ##STR108## taken alone or along withother flavoring additives may be dissolved in a suitable solvent such asethanol, pentane, diethyl ether and/or other volatile organic solventsand the resulting solution may either be sprayed on the cured, cased andblended tobacco material or the tobacco material may be dipped into suchsolution. Under certain circumstances, a solution of the mixture of cisand trans isomers of the compound having the structure: ##STR109## takenalone or taken together with other flavoring additives as set forthabove may be applied by means of a suitable applicator such as a brushor roller on the paper or leaf wrapper for the smoking product or it maybe applied to the filter by either spraying or dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have the compound havingthe structure: ##STR110## in excess of the amounts of concentrationsabove indicated so that when blended with other tobaccos, the finalproduct will have the percentage within the indicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic Virginia tobacco is sprayed with a 20% ethanolsolution of the compound having the structure: ##STR111## in an amountto provide a tobacco composition containing 400 ppm by weight of thecompound having the structure: ##STR112## on a dry basis. Thereafter thealcohol is removed by evaporation and the tobacco is manufactured intocigarettes by the usual techniques. The cigarette, when treated asindicated, has a desired and pleasing aroma (increased smoke bodysensation in the mouth with enhanced rich burley tobacco-like notes andpleasant aromatic nuances) which is detectable in the main and the sidestreams when the cigarette is smoked. This aroma is described as havingmusty, oily, slightly green, burley tobacco-like, full-bodied burleytobacco notes.

While our invention is particularly useful in the manufacture of smokingtobacco such as cigarette tobacco, cigar tobacco and pipe tobacco, othertobacco products formed from sheeted tobacco dust or fines may also beused. Likewise the compound having the structure: ##STR113## can beincorporated with materials such as filter tip materials, seam paste,packaging materials and the like which are used along with tobacco toform a product adapted for smoking. Furthermore, the compound having thestructure: ##STR114## can be added to certain tobacco substitutes ofnatural or synthetic origins (e.g. dried lettuce leaves) and,accordingly, by the term "tobacco" as used throughout thisspecification, is meant any composition intended for human consumptionby smoking or otherwise, whether composed of tobacco plant parts orsubstitute materials, or both.

The following Examples I-IX serve to illustrate the synthetic process ofour invention. The examples following Example IX serve to illustratethat aspect of our invention concerning the organoleptic utilities ofthe products produced according to the process of our invention. Theinvention is to be considered to be restricted thereto only as indicatedin the appended claims, however. All parts and percentages given hereinare by weight unless otherwise specified.

EXAMPLE I PREPARATION OF 2-ISOPROPYLACROLEIN

Reaction: ##STR115##

Into a 3-liter reaction flask equipped with thermometer, refluxcondenser, heating mantle and stirrer is placed 860 grams (10 moles) ofisovaleraldehyde. Over a period of thirty minutes, 65 grams (0.5 moles)of di-n-butylamine is added. The reaction mass exotherms to 48° C. and,with stirring, the reaction mass is heated to reflux at 85° C. Whilerefluxing over a period of 90 minutes while maintaining the temperatureof 83°-86° C., 900 grams (11.0 moles) of formaldehyde is added to thereaction mass. At the end of the addition of the formaldehyde, thereaction mass is refluxed for a period of 60 minutes. At the end of the60 minute period, the organic layer is washed with dilute hydrochloricacid, water, saturated sodium carbonate solution, and saturated saltsolution.

The crude material is then distilled through a 12" Goodloe columnyielding the following fractions:

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     Pressure                                                                             Fraction                                   Number    (°C.)                                                                          (°C.)                                                                            mm/Hg. (grams)                                    ______________________________________                                        1         20/37   40/42     100    183                                        2         37      44        100    165                                        3         40      52        100    180                                        4         30      150       100    213                                        5         90      210        3      88                                        ______________________________________                                    

FIG. 1 is the GLC profile for bulked fractions 1-4 of the foregoingdistillation (Carbowax column programmed at 100°-220° C. at 8° C. perminute).

FIG. 2 is the NMR spectrum for fraction 2 of the foregoing distillation(Solvent: CFCl₃ ; Field strength: 100 MHz).

The NMR spectrum is for the compound having the structure: ##STR116##

EXAMPLE II PREPARATION OF 2,6-DIMETHYL-5-METHYLENE-1-HEPTEN-4-OL

Reaction: ##STR117##

A mixture of magnesium turnings (146 grams) and tetrahydrofuran (2,000grams) is heated to reflux with vigorous agitation. To this mixture isadded a mixture of 3-chloro-2-methylpropene (500 grams), toluene (75grams), and 3-methyl-2-methylenebutanal (500 grams prepared according toExample I), at such a rate as to maintain reflux. The addition requiresapproximately four hours. The mass is stirred at reflux for 30 minutesand is then cooled to room temperature and quenched into excess ice cold10% aqueous acetic acid mixture. The organic layer is washedsuccessively with an equal volume of water, saturated sodium carbonatesolution and saturated salt solution. Rapid distillation at 3-12 mm/Hgpressure using a short column followed by careful redistillation (afterbulking) through a 12"×1" Goodloe packed column yields 580 grams of2,6-dimethyl-5-methylene-1-hepten-4-ol, boiling point range 73°-78° C.at 9 mm/Hg pressure.

The fractions yielded as a result of the short column distillation areas follows:

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     Pressure                                                                             Fraction                                   Number    (°C.)                                                                          (°C.)                                                                            mm/Hg. (grams)                                    ______________________________________                                        1         70/75   82/79     12/9   184                                        2         77      82        9.0    192                                        3         76      87        9.0    154                                        4         69      116       5.0     81                                        5         148     210       3.4     52                                        ______________________________________                                    

The fractions resulting from the total bulking and redistillationthrough the 12" Goodloe column are as follows:

    ______________________________________                                               Vapor    Liquid                Weight                                  Fraction                                                                             Vapor    Liquid  Pressure                                                                              Reflux                                                                              of Fraction                             Number (°C.)                                                                           (°C.)                                                                          mm/Hg.  Ratio (grams)                                 ______________________________________                                        1      57/73    77/78    9/9    9:1   59                                      2      74       78      9       9:1   78                                      3      74       78      9       9:1   81                                      4      74       78      9       9:1   37                                      5      74       80      9       9:1   82                                      6      74       80      9       9:1   31                                      7      74       81      9       9:1   85                                      8      74       95        8.5   9:1   82                                      9      78       168     9       9:1   74                                      10     50       210     3       9:1   11                                      ______________________________________                                    

FIG. 3 is the GLC profile for bulked fractions 5-7 of the foregoingGoodloe distillation (conditions: SE-30 column programmed at 100°-220°C.).

FIG. 4 is the NMR spectrum for fraction 3 of the foregoing Goodloedistillation consisting essentially of the compound defined according tothe structure: ##STR118## (Solvent: CFCl₃ ; Field strength: 100 MHz).

EXAMPLE III LARGE SCALE PREPARATION OF2,6-DIMETHYL-5-METHYLENE-1-HEPTEN-4-OL

Reaction: ##STR119##

A mixture of magnesium turnings (406 grams) and tetrahydrofuran (1,450grams) is heated to reflux and activated by the addition of a smallamount of VITRIDE®.

A mixture of 1,450 grams of 3-methyl-2-methylenebutanal (producedaccording to Example I) and 1,450 grams of methallyl chloride is addedover a four hour period at reflux. The mixture is stirred at reflux forone hour and then is cooled to room temperature. The resulting mixtureis poured slowly into approximately 3 kg of ice cold 50% acetic acidsolution. The organic layer is washed once with dilute acetic acid. Thetotal aqueous layer is then extracted with toluene. The combined organiclayers are then washed successively with water and with saturated sodiumbicarbonate solution. The solvent is recovered and the product isdistilled rapidly using a short column to give 1,457 grams of materialwhich GLC analysis shows contains 89.1% of2,6-dimethyl-5-methylene-1-hepten-4-ol having the structure: ##STR120##

EXAMPLE IV PREPARATION OF 2,6-DIMETHYL-5-METHYLENE-1-HEPTEN-4-YLACETOACETATE

Reaction: ##STR121##

Methyl acetoacetate (700 grams) is added over a period of one hour to amixture of xylene (1,300 ml), aluminum isopropylate (50 grams), and2,6-dimethyl-1-hepten-4-ol (683 grams, produced according to Example IIIsupra) at 100°-131° C. while distilling off the methanol through a 12"column packed with 1/4" porcelain saddles at a vapor temperature below70° C. The pot temperature is then increased to 150° C., anddistillation of the methanol is continued until the vapor temperaturereaches 95° C. (this takes approximately 4 hours). The reaction mass iscooled and poured into a mixture of crushed ice and 100 grams of 20%sulfuric acid solution.

The organic layer is then washed successively with water, saturatedsodium bicarbonate solution and 10% sodium chloride solution. Thesolvent is removed on a rotary evaporator at reduced pressure, and theproduct is distilled using a 24" Goodloe packed column to give 690 gramsof material which GLC analysis shows to contain 57%2,6-dimethyl-5-methylene-1-hepten-4-yl acetoacetate having thestructure: ##STR122##

EXAMPLE V(A) PREPARATION OF ISOSOLANONE(5-ISOPROPYL-8-METHYL-5,8-NONADIEN-2-ONE)

Reaction: ##STR123##

Into a 3 liter flask equipped with stirrer, thermometer, refluxcondenser and heating mantle is placed 500 grams ofN-methyl-2-pyrrolidinone and 10 grams of sodium carbonate. The resultingmixture is heated to 160° C., and over a period of one hour whilemaintaining the temperature at 160° C. with stirring, 1,310 grams of thecompound having the structure: ##STR124## prepared according to ExampleIV (57.7% purity) is added to the reaction mass. The reaction mass isthen refluxed at a temperature of 155°-170° C. for a period of 7 hours.At the end of this time, the reaction mass is cooled to roomtemperature.

An equal volume of water is added to the reaction mass. The reactionmass is then adjusted to a pH of 2 by addition of 10% sulfuric acid.

The reaction mass is filtered and washed two times with equal volumes ofwater. The toluene is stripped off and the reaction mass is rushed overusing a 1' short path column yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     Pressure                                                                             Fraction                                   Number    (°C.)                                                                          (°C.)                                                                            mm/Hg. (grams)                                    ______________________________________                                        1         62/66   91/100    4.0/3.2                                                                              109                                        2          84     122       3.0    213                                        3         103     145       3.6    134                                        4         135     224       5.5    196                                        5         148     235       3.6     43                                        ______________________________________                                    

Fractions 2-4 weighing 541 grams are bulked and then distilled on a 2'Goodloe column yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid                                                      Fraction  Temp.   Temp.      Pressure                                                                             Reflux                                    Number    (°C.)                                                                          (°C.)                                                                             mm/Hg. Ratio                                     ______________________________________                                        1         40/52   87/89      3.0/2.6                                                                              4:1                                       2         58       93        3.6    4:1                                       3         58       98        3.4    4:1                                       4         58      106        3.3    4:1                                       5         70      110        3.1    4:1                                       6         87      112        3.0    4:1                                       7         88      112        3.0    4:1                                       8         90      115        2.8    4:1                                       9         90      119        2.8    4:1                                       10        91      138        2.8    3:1                                       11        98      142        2.8    4:1                                       12        99      154        2.8    9:1                                       13        105     155        2.8    9:1                                       ______________________________________                                    

NMR, IR, mass spectral and GLC analysis yield the information that theresulting reaction product is a mixture of cis and trans isomers definedaccording to the structure: ##STR125##

FIG. 5 is the GLC profile for bulked fractions 7-11 of the foregoingdistillation (conditions: Carbowax column programmed at 100°-220° C.).

EXAMPLE V(B) PREPARATION OF 5-ISOPROPYL-8-METHYL-5,8-NONADIEN-2-ONE

Reaction: ##STR126##

A mixture of 500 grams of 2,6-dimethyl-5-methylene-1-hepten-4-ylacetoacetate prepared according to Example IV and 10 grams of aluminumtriisopropylate is heated to 150° C. at atmospheric pressure at whichpoint carbon dioxide gas begins evolving. The mixture is heated to195°-200° C. over a period of appoximately three hours and is then heldfor approximately 30 minutes at 195°-200° C. Carbon dioxide evolutionbecomes very slow at this point. The reaction mass is then cooled, andthe cooled reaction mass is poured into ice cold dilute aqueous aceticacid. The resulting organic layer is washed with water. The material isthen distilled through a 24" Goodloe packed column to yield 214 grams ofa material, b.p. 65°-94° C./3.2 mm/Hg. GLC analysis indicates that theproduct boiling over this range contains 84%5-isopropyl-8-methyl-5,8-nonadien-2-one as a mixture of cis and transisomers defined according to the structure: ##STR127##

EXAMPLE VI(A) PREPARATION OF ISOSOLANONE AND SOLANONE

Reaction: ##STR128##

Into a 100 ml reaction flask equipped with stirrer, thermometer andreflux condenser is placed 20 ml toluene, 0.5 grams ofpara-toluenesulfonic acid and 20 grams of5-isopropyl-8-methyl-5,8-nonadien-2-one having the structure: ##STR129##prepared according to Example V(B). The resulting mixture is stirred fora period of one hour at room temperature and then heated to 80°-82° C.and maintained at that temperature with stirring for a period of 8hours. At this point the resulting product contains four compounds; cisand trans isosolanone defined according to the structures: ##STR130## aswell as cis and trans solanone having the structures: ##STR131##

FIG. 6 is the GLC profile for the reaction product.

FIG. 7 is the NMR spectrum for peak 61 of the GLC profile of FIG. 6 forthe cis or trans isomer of the compound having the structure: ##STR132##

FIG. 8 is the NMR spectrum for the peak indicated by reference numeral"62" of FIG. 6 for the cis or trans isomer of the compound having thestructure: ##STR133##

EXAMPLE VI(B) PREPARATION OF 5-ISOPROPYL-8-METHYL-5,7-NONADIEN-2-ONE

Reaction: ##STR134##

A mixture of 250 ml of toluene, 1 gram of para-toluene-sulfonic acid and214 grams of 5-isopropyl-8-methyl-5,8-nonadien-2-one produced accordingto Example V is stirred for approximately 8 hours at reflux (120°-121°C.).

The resulting reaction mass is then cooled to room temperature andwashed with saturated sodium carbonate solution followed by 10% sodiumchloride solution.

The resulting reaction product is distilled through a 24" Goodloe packedcolumn yielding 141 grams of 5-isopropyl-8-methyl-5,7-nonadien-2-one asa mixture of cis and trans isomers.

EXAMPLE VII(A) PREPARATION OF 8-METHYL-5-ISOPROPYL-5,8-NONADIEN-2-ONE(ONE STEP REACTION FROM 2,6-DIMETHYL-5-METHYLENE-1-HEPTEN-4-OL)

Reaction: ##STR135##

Into a 250 ml reaction flask equipped with stirrer, thermometer, refluxcondenser and heating mantle is placed 52.0 grams (0.33 moles) of2,6-dimethyl-5-methylene-1-hepten-4-ol (bulked fractions 5-7 of thedistillation product of the reaction product prepared according toExample II), having the structure: ##STR136## 50 ml toluene and 2.0grams of aluminum triisopropylate.

The resulting mixture is heated with stirring to 40° C. under a nitrogenblanket, and over a period of 20 minutes. 45.0 grams (0.33 moles) ofmethyl acetoacetate is added to the reaction mass. At the end of theaddition the reaction mass is heated to reflux at 111°-120° C., andrefluxing is continued for a period of two hours. At the end of the twohour period a Bidwell trap is fitted to the reaction flask and 100 ml ofxylene is added to the reaction mass. The reaction mass is then heatedto reflux and sufficient solvent is distilled off to increase thereaction temperature to 127°-130° C. for a period of five hours. At theend of this period the reaction mass is cooled to room temperature.

FIG. 9 is the GLC profile for the reaction product of this examplecontaining the compounds having the structures: ##STR137##

The peak on the GLC profile indicated by reference numeral "91" is apeak analyzed as a mixture of compounds, one having the structure:##STR138## and the other having the structure: ##STR139##

FIG. 10 is the NMR spectrum for peak 91 of FIG. 9 analyzed as a mixtureof the compounds having the structures: ##STR140## (Solvent: CFCl₃ ;Field strength: 100 MHz).

EXAMPLE VII(B) PREPARATION OF 8-METHYL-5-ISOPROPYL-5,8-NONADIEN-2-ONE

Reaction: ##STR141## (wherein R represents ethyl).

Ethyl acetoacetate (176 grams) is added over a period of 20 minutes to amixture of toluene (250 ml), aluminum isopropylate (10 grams), and2,6-dimethyl-5-methylene-1-hepten-4-ol (prepared according to ExampleII; 205 grams) while maintaining the reaction mass at 115°-120° C.

While maintaining the reaction mass at a temperature of 115°-120° C. theresulting mixture is stirred for approximately 4 hours while distillingoff the ethanol produced. 100 ml of xylene is then added, and reflux iscontinued for approximately 2 hours. An additional 179 grams of ethylacetoacetate is added, and the mixture is heated at reflux (130°-137°C.) for a period of 6 hours. Heating is continued while removing lowboiling material until the pot temperature reaches 200° C. (which takesapproximately 2 hours) and then for an additional 1 hour at 200° C.

The reaction mass is then washed and distilled twice using a 36"×10 mmspinning band column to yield 113 grams of5-isopropyl-8-methyl-5,8-nonadien-2-one (mixture of cis and transisomers) defined according to the structure: ##STR142## b.p. 82°-84° C.at 2.5 mm/Hg, 90% pure by GLC analysis.

The distillation fractions from the first distillation are as follows:

    ______________________________________                                                  Vapor   Liquid                                                      Fraction  Temp.   Temp.      Pressure                                                                             Reflux                                    Number    (°C.)                                                                          (°C.)                                                                             mm/Hg  Ratio                                     ______________________________________                                        1         20/18   80/100     2.0/7.0                                                                              20:1                                      2         64      112        4.6    20:1                                      3         80      115        3.2    20:1                                      4         90      113        3.3    20:1                                      5         92      121        3.2    20:1                                      6         92      123        3.2    20:1                                      7         92      134        3.2    20:1                                      8         90      168        3.2    20:1                                      9         81      220        3.2    20:1                                      ______________________________________                                    

Fractions 4-8 weighing 127 grams are bulked and redistilled.

The distillation fractions from the second distillation are as follows:

    ______________________________________                                               Vapor    Liquid                Weight of                               Fraction                                                                             Temp.    Temp.   Pressure                                                                              Reflux                                                                              Fraction                                Number (°C.)                                                                           (°C.)                                                                          mm/Hg   Ratio (grams)                                 ______________________________________                                        1      58       90/95   2.6/2.8 20:1  11.0                                    2      82       100     2.7     20:1   7.0                                    3      83       102     2.7     20:1   7.0                                    4      84       102     2.6     20:1  11.0                                    5      84       103     2.6     20:1  10.0                                    6      84       103     2.6     20:1   8.0                                    7      84       103     2.6     20:1  10.0                                    8      84       103     2.4     20:1  25.0                                    9      84       103     2.4     20:1  12.0                                    10     84       109     2.4     20:1  14.0                                    11     60       140     2.4     20:1   9.0                                    ______________________________________                                    

FIG. 11 is the GLC profile for bulked fractions 4-11 of the foregoingdistillation (conditions: Carbowax column programmed at 100°-220° C.).

FIG. 12 is the NMR spectrum for fraction 7 of the foregoing distillationcontaining a mixture of cis and trans isomers of the compounds definedaccording to the structure: ##STR143## (Solvent: CFCl₃ ; Field strength:100 MHz).

FIG. 13 is the infra-red spectrum for fraction 7 of the foregoingdistillation containing a mixture of cis and trans isomers of compoundshaving the structure: ##STR144##

EXAMPLE VIII PREPARATION OF 5-ISOPROPYL-8-METHYL-5,8-NONADIEN-2-ONE

Reactions:

Reaction IIIA' ##STR145## Reaction IIIB ##STR146##

2,6-dimethyl-5-methylene-1-hepten-4-ol prepared according to Example II(875 grams; 93.6% by GLC analysis) is added over a one hour period to amixture of toluene (1,300 ml), methyl acetoacetate (700 grams) andaluminum triisopropylate (50 grams) while maintaining the reaction massat 110°-116° C.

The methanol which is generated is distilled off as formed using a 12"column packed with 1/4" porcelain saddles, with the vapor temperatureheld below 70° C. The reaction is heated for 7 hours at 120°-128° C.while continuing to collect the distillate at a vapor temperature below70° C. An additional 80 grams of methyl acetoacetate is then added, andthe reaction mass is heated to 156°-170° C. for 1 hour. The reactionmass is then cooled to room temperature and poured into aqueous sulfuricacid. The resulting organic layer is washed with water and then with a10% sodium chloride solution. Residual solvent is removed on a rotaryevaporator to yield 1,310 grams of crude2,6-dimethyl-5-methylene-1-hepten-4-yl acetoacetate having thestructure: ##STR147##

This crude ketoester is added over a period of 20 minutes to a mixtureof 10 grams of sodium carbonate and 500 grams ofN-methyl-2-pyrrolidinone while maintaining the reaction temperature at150°-160° C.

Immediate evolution of carbon dioxide is observed. The reaction mass isstirred for approximately 7 hours at 150°-170° C. at which time the rateof carbon dioxide evolution becomes very slow. The reaction mass iscooled and diluted with water. The pH is adjusted to 2 by addition of10% aqueous sulfuric acid solution. The reaction mass is filtered toremove solid material and the organic layer of the filtrate is washedtwice with water. Toluene is added to improve phase separation duringthis work-up. The solvent is recovered, and the crude product isdistilled twice to yield 243 grams of approximately 95% pure5-isopropyl-8-methyl-5,8-nonadien-2-one as a mixture of cis and transisomers defined according to the structures: ##STR148##

EXAMPLE IX PREPARATION OF 5-ISOPROPYL-8-METHYL-5,7-NONADIEN-2-ONE("ISOSOLANONE")

Reaction: ##STR149##

A mixture of 217 grams of the cis and trans isomers of5-isopropyl-8-methyl-5,8-nonadien-2-one prepared according to ExampleVIII (98% pure by GLC), 250 ml of toluene and 1 gram ofpara-toluenesulfonic acid is stirred for approximately 1 hour at 80°-85°C. and for approximately 7 hours at reflux (120°-124° C.).

The reaction mass is then cooled, and the cooled mixture is washedsuccessively with water and saturated sodium chloride solution. Theresulting material is then distilled twice to give 150 grams of5-isopropyl-8-methyl-5,7-nonadien-2-one boiling range 95°-109° C. at 33mm/Hg pressure which is 88.9% pure by GLC analysis. NMR analysis of thetwo major peaks indicates that they are cis and trans isomers.

The first distillation as indicated above yields the followingfractions:

    ______________________________________                                                 Vapor   Liquid           Weight of                                   Fraction Temp.   Temp.     Pressure                                                                             Fraction                                    Number   (°C.)                                                                          (°C.)                                                                            mm/Hg  (grams)                                     ______________________________________                                        1        34/40   48/56     75.0   51.0                                        2        40       58       70.0   39.0                                        3        35       65       70.0   41.0                                        4        32       70       5.0    4.0                                         5        84      100       2.6    6.0                                         6        92      104       2.6    22.0                                        7        100     112       2.4    86.0                                        8        100     147       2.4    69.0                                        9        106     180       2.4    4.0                                         ______________________________________                                    

Fractions 6-9 are bulked (weight 180 grams) and then re-distilled on a1' Goodloe column to yield the second distillation product having thefollowing fractions:

    ______________________________________                                                 Vapor   Liquid            Weight of                                  Fraction Temp.   Temp.      Pressure                                                                             Fraction                                   Number   (°C.)                                                                          (°C.)                                                                             mm/Hg. (grams)                                    ______________________________________                                        1        63/72   104/108    2.8/2.8                                                                              4.0                                        2         79     109        2.8    5.0                                        3         35     109        3.0    12.0                                       4         97     109        3.0    7.0                                        5         97     109        3.0    11.0                                       6         98     109        3.0    9.0                                        7        101     112        3.2    11.0                                       8        101     112        3.0    14.0                                       9        101     114        3.0    21.0                                       10       103     122        2.8    20.0                                       11       108     125        2.8    25.0                                       12       109     126        2.8    20.0                                       13       109     210        2.8    17.0                                       ______________________________________                                    

FIG. 14 is the GLC profile for bulked fractions 9-12 of the foregoingdistillation (conditions: SE-30 column programmed at 100°-220° C. at 8°C. per minute). The peak indicated by reference numeral "141" is thepeak for either the cis or trans isomer of isosolanone having thestructure: ##STR150##

The peak indicated by reference numeral "142" is for either the cis ortrans isomer of isosolanone having the structure: ##STR151##

FIG. 15 is the NMR spectrum for the peak indicated by reference numeral"141" of FIG. 14 for the cis or trans isomer of the isosolanone havingthe structure: ##STR152## (Solvent: CFCl₃ ; Field strength: 100 MHz).

FIG. 16 is the NMR spectrum for the peak indicated by reference numeral"142" of FIG. 14 for the cis or trans isomer of isosolanone having thestructure: ##STR153## (Solvent: CFCl₃ ; Field strength: 100 MHz).

EXAMPLE X

The following rose formulation is prepared:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Rhodinol              250                                                     Phenylethyl alcohol   195                                                     Alpha methyl ionone   80                                                      Linalyl acetate       60                                                      Cis-3-hexenyl acetate 5                                                       Jasmine absolute      10                                                      Cinnamic alcohol      20                                                      Rhodinyl acetate      60                                                      Cyclohexyl ethyl alcohol                                                                            20                                                      Geraniol              130                                                     Geranyl acetate       80                                                      Paraisopropyl cyclohexanol                                                                          60                                                       ##STR154##           30                                                      Trans, trans-delta damascone                                                                        10                                                      (10% in diethyl phthalate)                                                    ______________________________________                                    

A similar perfume is prepared without the trans,trans-delta-damascone.

The compound having the structure: ##STR155## with or without thetrans,trans-delta-damascone imparts minty, herbal, anisic, cedarleaf andpennyroyal-like nuances with corinander-like undertones to this floralcomposition. When the trans,trans-delta-damascone is added to thecomposition, it lends a sweet, floral, rose note to the fragrancecomposition in addition. The combination of thetrans,trans-delta-damascone and the compound having the structure:##STR156## gives rise to a very interesting synergistic effect on thisrose formulation making it much more intense and natural, fresh,Bulgarian rose-like.

EXAMPLE XI

One hundred grams of soap chips are intimately admixed with the variousperfumery substances set forth in Table I below. The resulting mixturesunder 8 atmospheres pressure, are heated to 180° C. and maintained atthat temperature and pressure under a nitrogen atmosphere for a periodof 3 hours. The resulting mass is then cooled and stamped into soapbars. Each of the soap bars prior to use and on use manifests aninteresting aroma as set forth in Table I below:

                  TABLE I                                                         ______________________________________                                        Perfumery Structure                                                                             Organoleptic Properties                                     ______________________________________                                        Compound having the structure:                                                                  A minty, herbal, anisic,                                     ##STR157##       cedarleaf and pennyroyal- like aroma with floral and                          coriander-like undertones.                                  prepared according to                                                         Example II, bulked fractions 3-8.                                             Perfume composition of                                                                          An intense floral aroma                                     Example X containing the                                                                        with minty, herbal, anisic,                                 compound having the structure:                                                                  cedarleaf, pennyroyal-like                                   ##STR158##       and coriander nuances and intense coriander                                   undertones.                                                 prepared according to Example                                                 II, bulked fractions 3-8, but                                                 not containing trans,trans-                                                   delta-damascone.                                                              Perfume composition of                                                                          A rose, floral aroma with                                   Example X containing both                                                                       minty, herbal, anisic,                                      the compound having the                                                                         cedarleaf and pennyroyal-                                   structure:        like topnotes and coriander                                  ##STR159##       undertones.                                                 prepared according to Example                                                 II, bulked fractions 3-8, and                                                 trans,trans-delta-damascone.                                                  ______________________________________                                    

EXAMPLE XII PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 grams oftalcum powder with 0.25 grams of one of the perfumery substances setforth in Table I of Example XI, supra. Each of the cosmetic powdersamples has an excellent aroma as set forth in Table I of Example XI,supra.

EXAMPLE XIII PERFUMED POLYMER

A melt of one hundred grams of polyethylene pellets is intimatelyadmixed under 100 atmospheres pressure with one of the perfumerysubstances set forth in Table I of Example XI, supra. The resulting meltis stirred with the perfumery substance under 100 atmospheres pressure,the percentage of perfumery substance in the melt being 12% by weight.The agitation is carried out in a stirred, high pressure, thick walled,pressure vessel containing baffles. At the end of the mixing period, theresulting plastic perfume concentrate is extruded in droplets throughorifices located in the apparatus whereby perfume-containing pellets areformed. The perfume-containing pellets are then molded into cores inaccordance with the procedure of application for U.S. Ser. No. 362,263filed on Mar. 26, 1982.

The resulting perfume-containing pellets exhibit perfumery properties asset forth in Table I of Example XI, supra. application for U.S. Ser. No.362,263 filed on Mar. 26, 1982 is hereby incorporated by referenceherein.

EXAMPLE XIV PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (which detergents are produced from thelysine salt of n-dodecyl benzene sulfonic acid as more specificallydescribed in U.S. Pat. No. 3,948,818 issued on Apr. 6, 1976, thespecification for which is incorporated by reference herein) areprepared containing the perfumery substances as set forth in Table I ofExample XI, supra. They are prepared by adding and homogeneously mixingthe appropriate quantity of the perfumery substance of Table I ofExample XI in the liquid detergent. The detergents all possess aromas asset forth in Table I of Example XI, the intensity increasing withgreater concentrations of perfumery substance as set forth in Table I ofExample XI, supra.

EXAMPLE XV PREPARATION OF COLOGNES AND HANDKERCHIEF PERFUMES

Perfumery substances set forth in Table I of Example XI are individuallyincorporated into colognes at concentrations of 1.0%, 1.5%, 2.0%, 2.5%,3.0%, 4.0% and 5.0% in 75%, 80%, 85% and 90% aqueous ethanol; and intohandkerchief perfumes at concentrations of 10%, 15%, 20%, 25% and 30%(in 85%, 90% and 95% aqueous ethanol). Distinct and definitive aromas asset forth in Table I of Example XI are imparted to the cologne and tothe handkerchief perfume samples.

EXAMPLE XVI

To the contents of a one pound can of HUNT'S® red beets at levels of 0.5ppm, 1 ppm and 2 ppm, the compound of Example II having the structure:##STR160## (distillation fraction 6) is added. The compound having thestructure: ##STR161## imparts to the canned red beets a much morenatural-like, freshly harvested beet flavor making them much moreorganoleptically pleasing.

EXAMPLE XVII GARLIC/ONION FLAVOR

The following ingredients are selected:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Methyl-propyl disulfide                                                                            2.0                                                      Methyl-propenyl disulfide                                                                          0.5                                                      Dipropyl-disulfide   86.0                                                      ##STR162##          7.0                                                      Propyl-propenyl disulfide                                                                          4.0                                                      Diallyl-disulfide    0.5                                                      ______________________________________                                    

The ingredients are thoroughly and homogeneously mixed at 25° C. Themixture has an excellent onion/garlic flavor definitely enhanced overthat obtained when the compound having the structure: ##STR163## isomitted. The resulting flavor is incorporated into natural onion oil,and the onion oil is added to a baked French bread under 2 atmospherespressure. The baked French bread has an interesting and novelonion/garlic nuance which is far improved over ordinary garlic oil oronion oil alone. It is noteworthy that no garlic oil is used herein.

EXAMPLE XVIII ONION/GARLIC FLAVOR COMPOSITION

The following mixture is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Dimethyl-disulfide      4                                                     Methyl-propyl disulfide                                                                              25                                                     Methy-propenyl disulfide                                                                              2                                                     Dipropyl-disulfide     30                                                      ##STR164##            15                                                     Diallyl-dislufide      16                                                     Propyl-propenyl disulfide                                                                             8                                                     ______________________________________                                    

The ingredients are thoroughly and homogeneously mixed at 25° C. Themixture has an excellent onion/garlic flavor definitely enhanced overthat obtained when the compound having the structure: ##STR165## isomitted.

EXAMPLE XIX

The composition of Example XVIII is dissolved in propylene glycol in anamount sufficient to give a propylene glycol solution containing 0.1% byweight of said mixture, and 0.9 cc of this solution is added to 7.3grams of a soup base consisting of:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Fine ground sodium chloride                                                                       35.62                                                     Hydrolyzed vegetable protein                                                                      27.40                                                     (4 BE:Nestle's)                                                               Mono sodium glutamate                                                                             17.81                                                     Sucrose             10.96                                                     Beef fat            5.48                                                      Sethness caramel color                                                                            2.73                                                      (powder B & C)                                                                ______________________________________                                    

The resulting mixture is added to 12 ounces of boiling water to create asoup having an excellent onion/garlic flavor.

A composition the same as that of Example XVIII is prepared except itcontains in addition, 5% by weight of natural garlic oil. When added tothe above soup base, and the mixture added to boiling water, a soup basehaving an excellent natural garlic/onion flavor is prepared having anovel, aesthetically pleasing taste and aroma.

EXAMPLE XX

0.5 grams of the mixture of Example XVII is emulsified in a solutioncontaining the following materials:

100 grams gum arabic

100 grams water

0.5 grams of a 20% solution in ethanol of butylated hydroxy anisole

The resulting emulsion is spray-dried in a Bowen Lab. Model spray-drier,inlet temperature 500° F., outlet temperature 200° F. Twelve grams ofthis spray-dried material is mixed with 29.2 grams of the soup base asset forth in Example XIX. The resulting mixture is then added to 12ounces of boiling water and an excellent onion/garlic flavored soup isobtained.

EXAMPLE XXI

330 grams of gelatin is dissolved at 40° C. in 8,250 grams of deionizedwater to form a "gelatin solution".

330 grams of a spray-dried gum arabic is dissolved at room temperaturein 8,250 grams of deionized water to form a "gum arabic solution".

The gum arabic solution is placed in a 30 liter vessel and 2.5 liters ofthe gelatin solution is added. The temperature of the mixture isadjusted to 37°-40° C. Through a tube beneath the surface of the gumarabic solution, 4,000 grams of a 0.1% (by weight) solution of themixture of Example XVIII and propylene glycol is added over a period ofapproximately 30 minutes.

The mixture is agitated at 37°-40° C. until an average droplet size of25 microns is obtained. The remaining gelatin solution (6 liters) isthen added. The pH of the solution is then adjusted to 4.5 to 4.6 with a10% sodium hydroxide solution.

After the 25 micron droplet size is achieved, the temperature is allowedto drop to 25° C. over a period of approximately 25 hours whilemaintaining the pH at 4.5 to 4.6

The capsule slurry is then stirred and cooled to 5° C. and is maintainedat 5° C. with stirring for at least 2.5 hours. The slurry is thenspray-dried.

The capsules thus formed are filtered and mixed with the soup base ofExample XIX in the weight ratio of 1:6. Twenty grams of the resultingcapsule-soup base mixture is then added to 30 ounces of boiling waterthereby creating a soup having an excellent onion/garlic flavor.

EXAMPLE XXII

The following ingredients are selected and mixed as described in ExampleXVIII and yield a composition having an excellent onion/garlic flavor.

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        A.   Methyl propenyl disulfide                                                                           5                                                       Methyl propenyl trisulfide                                                                          5                                                       3,4-dimethyl thiophene                                                                              1                                                       Dimethyl disulfide    12                                                      Dipropyl disulfide    32                                                       ##STR166##           44                                                 B.   Propyl propenyl disulfide                                                                           15                                                      Methyl propenyl disulfide                                                                           5                                                       Propyl propenyl trisulfide                                                                          5                                                       Dipropyl disulfide    10                                                      Corn oil              40                                                       ##STR167##           25                                                 C.   Methyl propenyl trisulfide                                                                          9                                                       Propyl propenyl trisulfide                                                                          9                                                       Propyl porpenyl disulfide                                                                           15                                                      Dimethyl disulfide    1                                                       Diallyl disulfide     1                                                       Gum arabic            40                                                       ##STR168##           25                                                 ______________________________________                                    

EXAMPLE XXIII TOBACCO FORMULATION

A tobacco mixture is prepared by admixing the following ingredients:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Bright          40.1                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue-cured)                                                                             14.2                                                          Glycerine       2.8                                                           Water           5.3                                                           ______________________________________                                    

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Ethyl butyrate 0.05                                                           Ethyl valerate 0.05                                                           Maltol         2.00                                                           Cocoa extract  26.00                                                          Coffee extract 10.00                                                          Ethyl alcohol  20.00                                                          Water          41.90                                                          ______________________________________                                    

The above stated tobacco flavor formulation is applied at the rate of1.0% to all of the cigarettes produced using the above tobaccoformulation. One-third of the cigarettes are then treated with 750 ppmof a 50:50 weight:weight mixture of trans,trans-delta-damascone producedaccording to Example X of U.S. Pat. No. 4,211,242, the disclosure ofwhich is incorporated by reference herein and the reaction product ofExample IX, bulked fractions 4-13 of the distillation product containinga mixture of cis and trans isomers of compounds having the structure:##STR169## Another third of the cigarettes is then treated with 750 ppmof a mixture of cis and trans isomers having the structure: ##STR170##produced according to Example IX, bulked fractions 4-13. The last thirdof the cigarettes are termed "control cigarettes", the controlcigarettes not containing either trans,trans-delta-damascone or thecompounds defined according to the structure: ##STR171## and theexperimental cigarettes which contain either the mixture oftrans,trans-delta-damascone and the compounds having the structure:##STR172## or the compounds having the structure: ##STR173## without thetrans,trans-delta-damascone are evaluated by paired comparison and theresults are as follows:

The experimental cigarettes both with and without thetrans,trans-delta-damascone are found to have more body and tobaccosmoke flavor and a fuller body sensation; much richer in body than thecontrol cigarettes.

The tobacco-like notes are enhanced in the experimental cigarettes, andthe flavor of tobacco, on smoking, is more aromatic with musty, slightlygreen, full-bodied burley tobacco notes. In addition, fruity notes andhay-tea-like aroma and taste nuances are added when thetrans,trans-delta-damascone is used.

The tobacco smoke flavor of the experimental cigarettes prior to smokinghas in the case of using the mixture of trans,trans-delta-damascone andthe mixture of cis and trans isomers having the structure: ##STR174## afloral, musty, hay-tea-like, sweet, slightly green, burley tobacco-likeand fruity aroma and taste profile.

All cigarettes are evaluated for smoke flavor with a 20 mm celluloseacetate filter.

What is claimed is:
 1. The compound having the structure: ##STR175## 2.The compound having the structure: ##STR176## wherein X is selected fromthe group consisting of chloro, bromo and iodo.
 3. The compound havingthe structure: ##STR177##